Method of manufacturing cottonseed oil

ABSTRACT

A METHOD OF MANUFACTURING COTTONSEED OIL, WHICH COMPRISES REMOVING 60-80% OF GOSSYPOL FROM THE COTTONSEED INTO THE COTTONSEED OIL, FOLLOWED BY SEPARATING THE GOSSYPOL FROM THE COTTONSEED OIL BY A SPECIFIC REAGENT, WHEREIN THE COTTONSEED IS CONDITIONED AND DECORTICATED, THE MEATS ARE CRUSHED, HEATED AND PROCESSED TO OBTAIN THE COTTONSEED OIL CONTAINING UP TO 2% OF GOSSYPOL AND THE SOLVENT CAKE CONTAINING FROM 0.2 TO 0.4% OF COMBINED GOSSYPOL AND UP TO 0.01% OF FREE GOSSYPOL, PROVISION BEING MADE FOR SUBJECTING THE COTTONSEED OIL AND SOLUTIONS THEREOF TO TREATMENT WITH AN AROMATIC AMINO ACID, SUCH AS ANTHRANILIC ACID.

United States Patent 3,654,325 METHOD OF MANUFACTURING COTTONSEED OIL Irina Andreevna Bashkutskaya, Raziezzhaya ulitsa 2, kv.

3; and Alla Borisovna Belova, Novo-Izmailovsky prospekt 19, kv. 57, both of Leningrad, U.S.S.R.; Semen Timofeevich Borschev, Ulitsa Karla Libknekhta 51; and Valentin Ivanovich Vlasov, Stroitelnaya ulitsa 1, kv. 41, both of Kokand, U.S.S.R.; Vasily Markovich Govor, Ulitsa imeni Usmana Jusupova 83; and Boris Idelevich Grinvald, Ulitsa Chimkentskaya 5, both of Tashkent, U.S.S.R.; Jury Alexeevich Zhabin, Ulitsa Pravdy 51, Kokand, U.S.S.R.; Yanina Andreevna Koneva, Ulitsa 40 let Oktyabrya 9, kv. 1; and Valentina Nikolaevna Popova, Kzhar Kurganskaya ulitsa 19, kv. 10, both of Tashkent, U.S.S.R.; Vladimir Petrovich Rzhekhin, Ulitsa Tjushina 3, kv. 5, Leningrad, U.S.S.R.; Vitaly Broneslavovich Rubnikovich, Ulitsa Litvinova 22; and Grigory Vladimirovich Rozeushtein, Ulitsa Pravdy 39, both of Kokand, U.S.S.R.; Alexandr Georgievich Sergeev, Ulitsa Tjushina 3, kv. 6; and Basya Yakovlevna Sterlin, Drezdenskaya ulitsa 20, kv. 29, both of Leningrad, U.S.S.R.; Usyaslav Iosifovich Trosko, Ulitsa Khalkabad 10; and Ravia Davlyatovna Sharipova, Massiv Chilanzar 1, kvartal 59, kv. 4, both of Tashkent, U.S.S.R.; Ivan Vasilievich Gavrilemco, Sofiiskaya naberezhnaya 33, korpus 3, kv. 97, Leningrad, U.S.S.R.; Semen Fedorovich Kiporenko, Dmitrovskoe shosse /1, kv. 67, Moscow, U.S.S.R.; and Anatoly Grigorievich Neschadim, Prospekt Slavy 19, korpus 1, kv. 199, Leningrad, U.S.S.R. No Drawing. Filed Apr. 23, 1969, Ser. No. 828,412

. Int. Cl. C09f 5 /02 U.S. Cl. 260-412.4 6 Claims ABSTRACT OF THE DISCLOSURE A method of manufacturing cottonseed oil, which comprises removing 60-80% of gossypol from the cottonseed into the cottonseed oil, followed by separating the gossypol from the cottonseed oil by a specific reagent, wherein the cottonseed is conditioned and decorticated, the meats are crushed, heated and processed to obtain the cottonseed oil containing up to 2% of gossypol and the solvent cake containing from 0.2 to 0.4% of combined gossypol and up to 0.01% of free gossypol, provision being made for subjecting the cottonseed oil and solutions thereof to treatment with an aromatic amino acid, such as anthranilic acid.

The present invention relates to oil seed processing and, more particularly, to processes for the manufacture of cottonseed oil, preferably from grades No. l and N0. 2 cottonseed (unblighted seed).

The currently employed methods for the manufacture of cottonseed oil make use of the preliminary expressionextraction technique or the direct extraction technique, wherein in order to inactivate gossypol, the toxic cottonseed pigment, by combining said pigment with cottonseed proteins, recourse is had to a vigorous heat and moisture treatment either during the initial (the former technique) or the terminal (the latter technique) stage of the process.

The aforesaid heat and moisture treatment improves somewhat the quality characteristics of cottonseed oil and soapstock lipids, but concomitantly brings about diverse detrimental chemical transformations which ultimately result in the loss of several highly beneficial components of the cottonseed. For example, vigorous heat and moisture treatments cause amino acids to irreversibly combine with gossypol and sugars, and this irreversible process entails a loss of 10-130% of the methionine and 10 -25% of the lysine and, therefore, decreases the nutritive value of cottonseed solvent cake. These losses amount to 18-40 3,654,325 Patented Apr. 4, 1972 thousand tons of lysine and 6-19 thousand tons of methionine annually.

The cottonseed solvent cake manufactured by the prior art methods requires further processing in order to inactivate the gossypol present therein, such as a treatment with aliphatic or aromatic amines or with an acetonehexane-water mixture.

The cottonseed oil obtained in accordance with the known methods must be subjected not only to alkaline refinement, but to adsorption refinement as well, and this refinement procedure involves additional losses and results in fat oxidation.

The known methods suffer from the further disadvantages of providing only a limited range of products and of being incapable of etficiently utilizing some highly useful cottonseed components. For example, the aforementioned methods do not make it possible to obtain gossypol-free cottonseed phosphatides and also to isolate gossypol, which is useful as an antioxidant, polymerization-inhibiting agent, etc.

The employment of these prior art methods causes gossypol losses of 120 to 160 thousand tons annually.

It is an object of the present invention to provide a method for the production of cottonseed oil which increases the yield and improves the quality of food cottonseed oil.

It is a further object of the present invention to provide a method for the production of cottonseed oil which makes it possible to preserve essential amino acids in the solvent cake.

It is a still further object of the present invention to provide a method for the production of cottonseed oil which makes it possible to obtain a number of novel useful nutritive or technical products, such as gossypol and gossypolfree phosphatides.

These and other objects have been accomplished by a method for the manufacture of cottonseed oil which comprises subjecting conditioned cottonseed to decortication, crushing the thus obtained meats, heating the crushed meats and thereafter obtaining cottonseed oil, solutions thereof in benzine or hexane, and a solvent cake, wherein, according to the invention, heating the crushed meats is carried out at a temperature of not greater than C. and the humidity of the crushed meats is maintained at 6.0 to 9.0% and in order to transfer 60-80% of the gossypol into the cottonseed oil or solutions thereof in benzine or hexane and to obtain a solvent cake containing from 0.2 to 0.4% of combined gossypol and not more than 0.01% of free gossypol.

According to the present method, it is expedient to subject the crushed cottonseed meat, prior to its being heated to a temperature of up to 90 C., to humidification, followed by maintaining the meat at a temperature of up to C. until the gossypol glandules undergo swelling, and thereafter carrying out the structurization without expressing the oil.

It is further expedient to treat the cottonseed oil containing up to 2% gossypol or solutions of the oil in benzine or hexane with an aromatic amino acid, e.g. anthranilic acid, at a temperature not higher than 90 C., the amount of the amino acid used being from 0.4 to 0.6% per one percent of the gossypol contained in the oil, and continuing the treatment under the aforesaid conditions until at least 80% of the gossypol is converted into the oil-insoluble form.

The present method contemplates separating the precipitate of the oil-insoluble gossypol from the oil or solutions thereof in benzine or hexane, treating the separated precipitate with benzine or hexane to extract and recycle the oil entrained with the precipitate and thereafter recovering the solvent from the defatted precipitate.

The method for the manufacture of cottonseed oil is carried out as follows.

The meats of unblighted cottonseed having a humidity of to are crushed and thereafter heated to 60-90" C., followed by pressing and extracting with benzine or hexane to obtain the oil containing up to 2% of gossypol, benzine or hexane solutions thereof, and also a solvent cake containing from 0.2 to 0.4% of combined gossypol and not more than 0.01% of free gossypol.

The aforesaid solvent cake and benzine or hexane solutions of oil may likewise be obtained by subjecting the crushed cottonseed meat to direct extraction. To do so, prior to being heated, the crushed meat should be humidified and maintained at a temperature of not greater than C. until the gossypol glandules undergo swelling, followed by structurizing the humidified crushed meat without oil expression, and thereafter extracting the oil with benzine or hexane.

This treatment causes 60-80% of the gossypol initially contained in the cottonseed to pass into the thus obtained oil and benzine or hexane solutions thereof and is like-wise instrumental in diminishing the losses of essential amino acids (the loss of lysine is decreased by 10'- 25% and that of methionine, by 10-30%) as a result of the marked inhibition of the reaction of amino acids with gossypol and sugars under the aforespecified condit1ons.

The oil produced from the cottonseed and containing up to 2% of gossypol or benzine or hexane solutions of the oil are treated with an aromatic amino acid, such as anthranilic acid, at a temperature of 6090 C. the amount of the amino acid used being 0.4 to 0.6% (as 100% acid) per each percent of the gossypol contained in the oil, and maintained under said conditions until as much as 80% of the gossypol initially contained in the oil is removed from the oil and solutions thereof in the form of a gossypol anthranilate precipitate. The removal of the gossypol from the cottonseed oil under the aforesaid conditions decreases the color index of the oil by a factor of 2 to 3, and brings about a diminution of the acid value and phosphatide content of the oil.

Anthranilic acid and the gossypol anthranilate formed are acidic compounds capable of reacting with alkalies, which reaction yields salts that are insoluble in the oil, but are readily soluble in water, so that traces of gossypol anthranilate and free anthranilic acid remaining in the oil after the anthranilate precipitate has been separated lend themselves to complete removal of the course of subsequent alkaline refining of the oil by any known technique. This caustic refining proceeds much more readily than does the alkali refining resorted to when processing the oil produced by known methods. The aforesaid caustic refining increases the yield of the refined cottonseed oil, decreases the color index of the oil to a maximum of 5 red units, as determined by the procedure adopted by the American Oil Chemists Society, and improves the quality of soapstock lipids (gossypol-free lipids) as evidenced by a lower color index and a decreased content of non-fat components.

The nutritive value of the edible cottonseed oil refined after the aforesaid treatment with anthranilic acid is superior to that of cottonseed oil subjected to conventional caustic refining.

The cake produced by pressing the cottonseed meat under the conditions disclosed hereinabove is crushed to obtain grit or it is processed into sturdy flakes, the grit or flakes being thereafter subjected to solvent extraction with benzine or other solvents, such as hexane, by a known technique to obtain a solvent cake with a gossypol content of up to 0.5%.

The benzine or hexane solutions of the oil obtained under the aforesaid conditions are treated with anthranilic acid, whereby from 80 to 95% of the gossypol initially contained in the solutions is removed therefrom, the treatment being carried out at a temperature of 6090 C. for a period of time required to convert the aforespeci'fied 4 percentage of the gossypol into an insoluble form. The amount of anthranilic acid used equals 04-06% (as 100% acid) per each percent of the gossypol contained in the solutions.

Upon gossypol removal, the benzine or hexane solutions of the oil are treated with water in order to separate gossypol-free phosphatides, the phosphatide precipitate being isolated by conventional procedures.

The solutions of the oil in benzine or hexane are next subjected to caustic refining, according to any one of the known methods, and thereafter the solvent is stripped off.

Caustic refining of the solutions of oil is likewise practicable when the solutions in question have not been treated with anthranilic acid and water.

Caustic refining of the oil solutions prepared as disclosed hereinabove markedly enhances the yield of the oil, the color index of the cottonseed oil thus obtained being much lower than that of the oil refined by conventional techniques.

Gossypol-free phosphatides obtained by treating the oil solutions as described above and soapstock lipids which result from caustic refining of both the oil and the solutions thereof are incorporated to the extent of l to 10% into the solvent cake, and the enriched solvent cake is granulated by a conventional technique or may be used in the non-granulated state. The above process for the production of the solvent cake enhances the feed value of the cake, improves the conditions of cake granulation, decreases the consumption of power required for granulating the cake, diminishes losses during solvent cake shipment, and also provides for a more efiicient employment of the granulated solvent cake because of higher swelling capacity and optimum mechanical strength of the cake granules.

T 0 remove the precipitate of gossypol anthranilate obtained as a result of treating the oil as well as the solutions thereof with anthranilic acid, recourse may be had to the known filtering techniques and equipment. The precipitate entrains some oil and phosphatides, but subsequent defatting of the gossypol anthranilate with solvents, such as benzine and hexane, makes it possible to recycle the cottonseed oil and phosphatides entrained with the precipitate.

Upon defatting, the gossypol anthranilate is obtained in the form of a tasteless and odorless orange powder that contains 45-55% gossypol combined with anthranilic acid and l-1.5% combined phosphorus. This product lends itself to direct use in the chemical industry as an antioxidant in conjunction with diverse materials, or may be employed for recovering therefrom commercial gossypol in a yield of 35-50% by weight of the anthranilate and anthranilic acid in a yield of l0-15 by weight of the anthranilate. The anthranilic acid thus recovered may be recycled.

The process conditions disclosed hereinbelow pertain to the preferred embodiment of the present invention, other embodiments thereof being, however, practicable. The present method may be accomplished by using diverse types of process equipment and, accordingly, the process conditions may be varied within the ranges indicated hereinabove in the description of the method claimed in the present invention.

EXAMPE 1 The decorticated cotton seeds (meats) having a moisture content of 9.0% are comminuted until 70% of the crushed meats remains on a sieve with 1 mm. openings. Then the crushed meats, without additional humidification or steaming, are heated to a temperature of :5 C- to attain a moisture content of 8% and pressed in screw expellers.

The oil obtained by the pre-pressing technique contains 12% gossypol and 0.8-1.2% phosphatides as against 0.100.30% gossypol and 1.4-1.75% phosphatides contained in the oil obtained by the known methods.

The cotton seed oil produced during the pre-pressing stage is treated, while being stirred with anthranilic acid (dry acid or inthe form of a suspension in oil) taken in an amount of 0.53% (calculated as 100% acid) per each percent of the gossypol contained in the oil to be treated the temperature of the mixture being maintained at 85 C. for a period of 6 hours until there is formed a gossypol anthranilate precipitate, followed by cooling the mixture and separating the precipitate by conventional techniques, such as filtration, centrifuging or separation. Listed in Table 1 are the quality characteristics of the oil prior to and after gossypol removal by means of anthranilic acid.

"In the oil treated with anthranilic acid, the gossypol is present combined with the anthranilic acidas gossypol anthranilate.

It follows from Table 1 that the content of phosphatides in the cotton seed oil obtained during the pre-pressing stage and treated with anthranilic acid as described hereinabove falls to 0.1-0.3% because of phosphatide entrainment 'with the gossypol anthranilate precipitate (6070% ofthe phosphatides entrained are in the form of a compound obtained as a result of the reaction between anthranilic acid and monosubstituted gossyphosphatides, and 20- 30% is adsorbed on the gossypol anthranilate precipitate). The adsorbed phosphatides pass into the solutions of oil in benzine when the gossypol anthranilate is subjected to defatting, thereby increasing the content of phosphatides in the oil solutions prior to their being treated with water.

Upon separation of the gossypol anthranilate precipitate, the cotton seed oil is subjected to caustic refining by a known technique.

As a result of the above treatment, the cotton seed oil lends itself readily to caustic refining, the yield of the oil increases by 1.5-2.5%, while the color index of the oil becomes as low as 5 red units, according to the test procedure of the American Oil Chemists Society.

The cake produced during the pre-pressing stage under the conditions disclosed hereinabove is comminuted until all the comminuted material passes through a sieve having 12 mm. openings, the amount of the particles passing through a sieve with 1 mm. openings being 4% maximum. The cake may also be processed by a known technique to obtain sturdy flakes.

From the grit or. flakes thus obtained, the oil and residual gossypol are extracted with benzine by a known technique; and. the residual material comprises the solvent cake containing not more than 0.5% of gossypol.

The oilsolution containing 60% oil is treated at a temperature of 80i5 C., while being stirred, with anthranilic acid taken in an amount of 0.53% per each percent of the gossypol contained'therein and maintained under said conditions forZ-hours until a gossypol anthranilate precipitate is formed, followed by cooling down the benzine solution of the oil and separating the precipitate by a known technique. The aforesaid conditions are conductive to removing asmuch as 80-95% of the gossypol initially contained in the 011 solution.-

The gossypol anthranilate isolated from the oil or the solution thereof and containing from 30 to 60% oil is subjected to defatting with benzine by a known procedure, which process step makes possible the recycling of from 1.5 to 3.0% of thelipids which have been adsorbed by the anthranilate precipitate, the yield of defatted anthranilate being l to 2% by weight of the oil.

The benzine solution of the oil obtained as a result of defatting the gossypol anthranilate is combined with the oil solution bulk from which the gossypol has been previously removed, followed by treating the mixture of the solutions with water taken to the extent of 3% and separating the resultant flufiy precipitate of phosphatides, and thereafter refining the benzine solution of the oil and stripping off the solvent.

The removal of gossypol and phosphatides and refining the oil solution result in increasing the yield of the refined oil by 4-5 and in diminishing the color index by 2-4 red units as compared with the color index of the extracted cotton seed oil subjected to conventional caustic refining. The gossypol is likewise removed from the soapstock lipids.

The gossypol-free phosphatides and soapstock lipids are incorporated into the solvent cake in an amount adequate to obtain an overall lipid content in the solvent cake of 4-5%. From the solvent cake the solvent is thereafter removed by a conventional procedure.

Presented in Table 2 are the characteristics of the solvent cake obtained by the present method and, by way of comparison, those of the solvent cake produced by the known method.

TABLE 2 Solvent cake Present Known method method 7. 2-9. 0 8. 0-9. 0 Traces-0. 010 0. 010-0. 020 0. 20-0. 40 0. -1. 00

Property Where the solution of oil in benzine obtained by extracting the cake is not treated with anthranilic acid and water, the process of producing refined cottonseed oil by the prepressing technique proceeds as disclosed in Example 1, and the oil solution is subjected to caustic refining with an aqueous alkaline solution containing from to 500 grams of alkali per liter, the amount of the alkali used being 5 to 12 kg. per ton of the oil, depending upon the acid value of the oil. Caustic refining is carried out continuously at a temperature of 5565 C., followed by maintaining the oil in the caustic solution for 1 hour, subjecting the resultant mixture to hydration, and thereafter separating the soapstock lipids from the refined oil solution by a conventional technique.

Caustic refining of the oil solution under the conditions disclosed hereinabove results in the obtention of refined oil having a color index (based on oil) of from 7 to 10 red units at 35 yellow units in a 13.5-cm. layer, an acid value, 0.1 to 0.25 mg. KOH, foots, 0.02 to 0.08%, without soap traces. The solvent is separated from this solution by a conventional technique.

The refined and extracted oil obtained upon stripping off the solvent has the following characteristics: flash point, 235 to 245; foots, 0.02 to 0.1%, and moisture content, 0.2 to 0.4%. The cottonseed oil thus obtained is subjected to vacuum drying to attain a moisture content of 0.02-0.1% and is thereafter filtered.

Carrying out the process under the conditions disclosed hereinabove makes it possible to obtain cottonseed oil exhibiting the following characteristics: color index, from 6 to 9 red units at 35 yellow units in a 13.5-cm. layer; acid value, 0.1 to 0.3 mg. KOH; moisture content, 002 to 0.09%.

Benzine is removed by a known technique from the resultant soapstock lipids which contain 1.5 to 15% of neutral fat at a total fat content of 40-50% and 6 to 15% of benzine. The soapstock lipids, in which the ultimate benzine content equals about 0.5%, the fatty acid components are close to those of the cottonseed oil, and the phosphatides and tocopherols are abundant, are hydrated until the moisture content equals 55-65% and thereafter mixed with the solvent cake at a temperature of 80l00 C. for a period of -30 minutes. The soapstock lipids are incorporated into the solvent cake to the extent of 3-5%.

EXAMPLE 2 The decorticated cotton seeds (meats) having a moisture content of 9% are crushed and thereafter humidified until the moisture content reaches 15%, maintained at a temperature of not greater than 35 C. to bring about swelling of the gossypol glandules, followed by structurization without oil expression to obtain 0.1-0.2 mm. thick. The thus obtained flakes are seasoned at a temperature of 50i5 C. to reduce the moisture content to 8-9% and then extracted, the solvent used in the initial extraction stages being cottonseed oil-in-benzine solutions containing at least of oil. The extraction is carried out in a multistage extractor and yields cottonseed oil-in-benzene solutions containing up to 2% of gossypol. Upon solvent removal, in the solvent cake, the content of bound gossypol does not exceed 0.4%, and that of free gossypol equals 0.01%.

The thus obtained cottonseed oil-in-benzene solution is subjected to further treatment which is analogous to the treatment described in Example 1.

We claim:

1. A method for the manufacture of cottonseed oil, said method comprising conditioning and decorticating cottonseed, crushing the meats, heating the crushed meats to a temperature of not higher than 90 C. and simultaneously humidifying the crushed meats to a humidity of 6-9% in order to ensure maximum extraction of gossypol from the crushed meats, thereafter pressing the meats and extracting same with benzine or hexane to obtain cottonseed oil containing up to 2% of gossypol, a cottonseed oil-in-benzine or hexane solution, and a solvent cake containing from 0.2 to 0.4% of combined gossypol and not more than 0.01% of free gossypol.

2. A method for the manufacture of cottonseed oil, said method comprising conditioning and decorticating cottonseed, crushing the meats, humidifying and maintaining the crushed meats at a temperature of not higher than C. until the gossypol glandules swell, subjecting the crushed and humidified meats to structurization without expressing the oil, seasoning the crushed meats at a temperature of up to 90 C. to bring the crushed meats to a humidity of 69%, and thereafter removing from the crushed meats, a maximum amount of gossypol with the oil by extracting the meats with benzine or hexane,

the initial extraction stages being carried out by means of a hot concentrated solution of the cottonseed oil in benzine or hexane.

3. A method for the manufacture of cottonseed oil, said method comprising conditioning and decorticating cottonseed, crushing the meats, heating the crushed meats to a temperature of not higher than 90 C. and simultaneously humidifying the crushed meats to a humidity of 69% in order to ensure maximum extraction of gossypol from the crushed meats, thereafter pressing the meats and extracting same with benzine or hexane to obtain cottonseed oil containing up to 2% of gossypol, a cottonseed oil-in-benzine or hexane solution, and a solvent cake containing from 0.2 to 0.4% of combined gossypol and not more than 0.01% of free gossypol; and then treating the cottonseed oil containing up to 2% of gossypol and the cottonseed oil-in-benzine or hexane solution with anthranilic acid, at a temperature of up to 90 C., in the amount of 0.4 to 0.6% per each percent of gossypol contained in the cottonseed oil and continuing the treatment for a period of time sufficient to convert at least of the gossypol into the oil-insoluble state.

4. A method for the manufacture of cottonseed oil, said method comprising conditioning and decorticating cottonseed, crushing the meats, humidifying and maintaining the crushed meats at a temperature of not higher than 35 C. until the gossypol glandules swell, subjecting the crushed and humidified meats to structurization without expressing the oil, seasoning the crushed meats at a temperature of up to C. to bring the crushed meats to a humidity of 69%, and thereafter removing from the crushed meats, a maximum amount of gossypol with the oil by extracting the meats with benzine or hexane, the initial extraction stages being carried out by means of a hot concentrated solution of the cottonseed oil in benzine or hexane and then treating the cottonseed oil-in-benzine or hexane solution with anthranilic acid, at a temperature of up to 90 C., in the amount of 0.4 to 0.6% per each percent of the cottonseed oil and continuing the treatment for a period of time sufficient to convert at least 80% of the gossypol into the oil-insoluble state.

S. A method according to claim 3, wherein the gossypol converted into the insoluble state is separated in the form of a precipitate from the cottonseed oil and cottonseed oilin-benzine or hexane solution, followed by treating the separated precipitate with benzine or hexane to extract and recycle the cottonseed oil contained therein, and thereafter stripping off the solvent from the defatted precipitate.

6. A method according to claim 4, wherein the gossypol converted into the insoluble state is separated in the form of a precipitate from the cottonseed-in-benzine or hexane solution, followed by treating the separated precipitate with benzine or hexane to extract and recycle the cottonseed oil contained therein, and thereafter stripping off the solvent from the defatted precipitate.

References Cited p UNITED STATES PATENTS 2,484,831 10/1949 Hutchings et al. 260412.4 2,629,722 2/1953 Dunning 260412.4 2,726,253 12/1955 Gastrock et a1. 26 0412.4

LEWIS GOTTS, Primary Examiner J. R. BROWN, Assistant Examiner Patent No. 3,654,325 Dated Avril 441972 Inventor(s) IRINA ANDREEVNA BASHKUTSKAYA e; a].

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 1, line 10: after soiution" insert -containing up to 2% gossypol- Claim 3 iine 10: after solution insert --containing up to 2% of gossypo1-- Claim A, line 17: after of insert "the gossypol Signed and sealed this 29th day of May, 1973.

LSEAL) Attestz EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents USCOMM-DC-60376-P69 *1 us. GOVERNMENT PRINTING ornctt': was osse-as4 FORM PO-105O (10-69) 

